EP4076336B1 - Zahnwurzelkanalfüllungszusammensetzung - Google Patents

Zahnwurzelkanalfüllungszusammensetzung Download PDF

Info

Publication number
EP4076336B1
EP4076336B1 EP20833819.4A EP20833819A EP4076336B1 EP 4076336 B1 EP4076336 B1 EP 4076336B1 EP 20833819 A EP20833819 A EP 20833819A EP 4076336 B1 EP4076336 B1 EP 4076336B1
Authority
EP
European Patent Office
Prior art keywords
paste
root canal
canal filling
filling composition
dental root
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20833819.4A
Other languages
English (en)
French (fr)
Other versions
EP4076336A1 (de
Inventor
Joachim E. Klee
Matthias Worm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dentsply Detrey GmbH
Dentsply Sirona Inc
Original Assignee
Dentsply Detrey GmbH
Dentsply Sirona Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dentsply Detrey GmbH, Dentsply Sirona Inc filed Critical Dentsply Detrey GmbH
Publication of EP4076336A1 publication Critical patent/EP4076336A1/de
Application granted granted Critical
Publication of EP4076336B1 publication Critical patent/EP4076336B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/50—Preparations specially adapted for dental root treatment
    • A61K6/54—Filling; Sealing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/78—Pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/898—Polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the present invention relates to a dental root canal filling composition, the use of such a dental root canal filling composition for a treatment or a prevention of an endodontic disease.
  • the present invention is further directed to a storage-stable two-pack dental root canal filling composition making use of such an inventive dental root canal filling composition.
  • a polymerizable dental composition may be a dental adhesive composition, a bonding agent, a pit and fissure sealant, a dental desensitizing composition, a pulp capping composition, a dental composite, a dental glass ionomer cement, a dental cement, a dental root canal sealer composition, a root canal filling composition, or a dental infiltrant.
  • Dental compositions are desired to approach natural tooth structure with regard to strength and appearance. Accordingly, a great effort is documented by the prior art, which is directed to the development of dental compositions having improved properties with regard to physical properties, biocompatibility, aesthetics and handling properties.
  • Dental compositions selected from a root canal filling composition and a pulp capping composition are subject to additional requirements in that the cured product is required to have a high radiopacity and in that the composition may not require external irradiation for curing. Moreover, it is desirable that the composition adheres to the wall of the root canal in order to further improve the tight sealing of the dental root canal. Given that the shape of the root canal may change as a result to mastication and temperature changes, the cured composition must tolerate such changes without compromising a tight seal of the root canal.
  • a root canal filling composition or pulp capping composition contains radiopaque particulate fillers dispersed in a curable matrix.
  • the dispersion of radiopaque particulate fillers gives rise to a stability problem of the dispersions due to the high density of the filler and the low viscosity of the curable matrix.
  • the composition is cured by a thermal curing mechanism which may involve step growth polymerizing epoxide precursor compounds.
  • a thermal curing mechanism which may involve step growth polymerizing epoxide precursor compounds.
  • the gold standard of dental root canal filling material which presently offers the best overall properties, is AH Plus ® from (Dentsply DeTrey, Konstanz/Germany).
  • the good overall properties of AH Plus ® especially concern physical and thermo-mechanical properties, curing properties like gelation time and handling properties like flow- and viscosity properties.
  • the good overall properties highly depend on the used filler composition and the structure of the epoxide-amine addition polymer, which is formed during the curing process of the AH Plus ® composition.
  • the AH Plus ® dental root canal filling composition consists of an amine paste and an epoxide paste.
  • the AH Plus ® epoxide paste comprises Bisphenol A diglycidylether ( CAS: 25068-38-6 ) as a main ingredient and the AH Plus ® amine paste comprises the diamine N,N'-dibenzyl-5-oxanonandiamin-1,9 (OPC-91, CAS: 113506-22-2 ) and the monoamine 1-aminoadamantane ( CAS: 768-94-5 ) as main ingredients.
  • OPC-91, CAS: 113506-22-2 diamine N,N'-dibenzyl-5-oxanonandiamin-1,9
  • monoamine 1-aminoadamantane CAS: 768-94-5
  • US 2019/020940 A1 describes dental compositions comprising at least two di- or polyepoxides, one or more primary monoamines and/or disecondary diamines, and one or more aliphatic polyamines.
  • thermomechanical properties of AH Plus have crucial impact on the performance of a dental root canal filling composition.
  • a dental root canal filling composition which shall exhibit a glass transition temperatures T g in the range of 40 to 50°C and gelation times at body temperature below 16 h.
  • claim 7 refers to the use of such a dental root canal filling composition for a treatment or a prevention of an endodontic disease.
  • Claim 8 describes a storage-stable two-pack dental root canal filling composition.
  • the present invention accordingly provides a dental root canal filling composition
  • a dental root canal filling composition comprising
  • the present invention offers alternative primary monoamines which can withstand any toxicological concerns while at the same time especially the characteristic thermomechanical properties of AH Plus can be maintained.
  • present invention provides a dental root canal filling composition, which exhibits a glass transition temperature T g in the range of 40 to 50°C and a gelation time at body temperature below 16 h.
  • substantially free means in the context of the present invention a concentration of less than 5 weight percent, preferably less than 2.5 weight percent, and more preferably less than 1 weight percent based on the total weight of the dental root canal filling composition.
  • the present invention is based on the recognition that a dental root canal filling composition comprising a primary monoamine as claimed provides a dental root canal filling composition, which has comparable and/or improved overall properties compared to the AH Plus ® composition.
  • a dental root canal filling composition comprising such a primary monoamine as claimed, namely, 1-aminotetraline
  • a dental root canal filling composition having excellent properties with regard to physical and mechanical properties, biocompatibility, aesthetics and handling properties, having a high radiopacity, a high storage stability, a low shrinkage and flexibility, a relatively short setting time, and may be cured in the absence of light.
  • the dental root canal filling composition according to the present invention provides adjustable working and setting times, suitable viscosity, and shows no coloration problems.
  • a primary monoamine according to the present invention is adapted to act as a monomer which offers excellent reactivity, so that a dental root canal filling composition having excellent curing properties is provided. Furthermore, the use of the primary monoamine according to the present invention leads to a polymer having comparable and/or improved overall properties compared to the final polymer of the AH Plus ® composition.
  • the present invention relates to a dental root canal filling composition comprising a specific primary monoamine.
  • a dental root canal filling composition in accordance with the invention is adapted to form epoxide-amine addition polymers.
  • the dental root canal filling composition in accordance with the present invention is polymerizable and polymerizes to form a thermoplastic polymer.
  • polymerization and “polymerizable” relate to the combining by covalent bonding of a large number of smaller molecules, such as monomers, to form larger molecules, that is, macromolecules or polymers.
  • the monomers may be combined to form only linear macromolecules, or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
  • difunctional monomers form linear polymers
  • monomers having at least three functional groups form crosslinked polymers also known as networks.
  • the amount of leachable monomers can be significantly reduced.
  • curing means the polymerization of functional polymerizable compounds such as monomers, oligomers or even polymers, into a polymer network, preferably a crosslinked polymer network.
  • curable refers to dental composition that will polymerize upon mixing.
  • the working time is a period of time, measured from the start of mixing, during which it is possible to manipulate the root canal sealer.
  • the setting time is a period of time measured from the end of mixing at (37 ⁇ 1) °C and not less than 95 % relative humidity until the sealer does not show a mechanical impression using a Gilmore-type metric indenter.
  • the term "storage stability” as used herein means that the dental composition keeps its characteristics, in particular its working time and setting time, even after a long storage time of for example about 2 years.
  • the inventive primary monoamine is 1-aminotetraline:
  • the at least one diamine of the dental root canal filling composition is a disecondary diamine or a primary diamine, wherein preferably the dental root canal filling composition comprises at least one primary diamine and at least one disecondary diamine.
  • a primary diamine in the context of the present invention is preferably a primary aliphatic diamine according to the following formula (III): wherein
  • Q' represents a substituted or unsubstituted C 3-20 cycloalkylene group, more preferably Q' represents a substituted cycloalkylene group, and even more preferably Q' represents a substituted cycloalkylene group, wherein the substituents may be one or more C 1-6 alkyl groups, C 3-12 cycloalkyl groups.
  • the dental composition according to the present invention comprises a primary aliphatic diamine, which is selected from the group consisting of octahydro-4,7-methano-1H-indenedimethylamine ( CAS: 68889-71-4 ) and isophorone diamine ( CAS: 2855-13-2 ).
  • a disecondary diamine in the context of the present invention is preferably a disecondary diamine according to the following formula (IV): wherein
  • A is a divalent substituted or unsubstituted C 2-30 hydrocarbyl group, which may contain up to 10 heteroatoms selected from the group consisting of N, O, S, Si.
  • A is a divalent unsubstituted C 2-30 hydrocarbyl group.
  • A is a divalent substituted C 2-30 hydrocarbyl group, wherein the substituents are selected from the group consisting of a hydroxyl group, a tertiary amine group, a halogen atom, a C 1-6 alkyl group, a C 3-10 cycloalkyl group, a C 1-6 alkoxy group, a C 5-10 aryl group, a C 6-11 arylalkyl group.
  • A represent a divalent substituted or unsubstituted C 2-30 hydrocarbyl group, wherein the C 2-30 hydrocarbyl group is a C 2-30 alkylidene group, a C 3-10 cycloalkylidene group, a C 7-30 arylalkylidene group.
  • R 3 and R 4 which may be the same or different, independently represent C 1-10 alkyl group, a C 3-10 cycloalkyl group, or a C 6-11 arylalkyl group.
  • the C 1-10 alkyl group, the C 3-10 cycloalkyl group, or the C 6-11 arylalkyl group may be substituted or unsubstituted.
  • the C 1-10 alkyl group, the C 3-10 cycloalkyl group, or the C 6-11 arylalkyl group is unsubstituted.
  • the substituents are selected from the group consisting of a hydroxyl group, a tertiary amine group, a halogen atom, a C 1-6 alkyl group, a C 3-10 cycloalkyl group, a C 1-6 alkoxy group, a C 5-10 aryl group, or a C 6-11 arylalkyl group.
  • the dental composition according to the present invention comprises a disecondary diamine selected from the group consisting of N,N'-dibenzylethylenediamine, N,N'-dibenzyl-3,6-dioxaoctandiamine-1,8, N,N'-dibenzyl-5-oxanonandiamine-1,9 ( CAS: 113506-22-2 ), N,N'-dibenzyl-(2,2,4)trimethylhexamethylendiamine, N,N'-dibenzyl-(2,4,4)trimethylhexamethylendiamine, N,N'-dibenzylcyclohexylenediamine, N,N'-dibenzyl-xylylenediamine.
  • a disecondary diamine selected from the group consisting of N,N'-dibenzylethylenediamine, N,N'-dibenzyl-3,6-dioxaoctandiamine-1,8, N,N'-dibenz
  • the dental root canal filling composition further comprises at least one rheological additive and/or rheological modifier, such as ethyl cellulose and cellulose acetate butyrate.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste or the epoxide paste comprises at least one rheological additive and/or rheological modifier.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one rheological additive and/or rheological modifier.
  • the at least one rheological additive and/or rheological modifier is a cellulose derivate, which is selected from the group consisting of cellulose ether and cellulose ester.
  • ethyl cellulose ( CAS 9004-57-3 ) as cellulose ether and cellulose acetate butyrate ( CAS 9004-36-8 ), cellulose acetate propionate ( CAS 9004-39-1 ), cellulose acetate ( CAS 9004-35-7 ) or cellulose propionate ( CAS 9004-48-2 ) as cellulose ester are especially preferred.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one rheological additive and/or rheological modifier; wherein the amine paste comprises at least one rheological additive and/or rheological modifier, which is a cellulose ether, preferably ethyl cellulose; and wherein the epoxide paste comprises at least one rheological additive and/or rheological modifier, which is a cellulose ester, preferably cellulose acetate butyrate.
  • Cellulose ethers are especially preferred in the amine paste because under certain circumstances, mainly depending on the overall composition of the respective amine paste, cellulose esters could cause in exceptional cases problems due to a possible undesired side reaction between the cellulose ester molecules and the reactive amine groups.
  • the dental root canal filling composition further comprises at least one filler, which is not a radio-opaque particulate filler.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste or the epoxide paste comprises at least one filler, which is not a radio-opaque particulate filler.
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one filler, which is not a radio-opaque particulate filler.
  • the at least one filler which is not a radio-opaque particulate filler, is a fumed silica, which is selected from the group consisting of Aerosil ® 200, Aerosil ® R805 ( CAS 92797-60-9 ), Aerosil ® R202 ( CAS 67762-90-7 or CAS 541-02-6 ), CAB-O-SIL TS 720 ( CAS 67762-90-7 ), Aerosil ® R8200 ( CAS 68909-20-6 ), Aerosil ® R812 ( CAS 68909-20-6 ), Aerosil ® R972 ( CAS 68611-44-9 ), and Aerosil ® R974 ( CAS 68611-44-9 ).
  • the dental root canal filling composition comprises an amine paste and an epoxide paste; wherein the amine paste and the epoxide paste each comprises at least one filler, which is not a radio-opaque particulate filler; wherein the amine paste comprises at least one filler, which is not a radio-opaque particulate filler, which is Aerosil ® 200; and wherein the epoxide paste comprises at least one one filler, which is not a radio-opaque particulate filler, which is a fumed silica selected from the group consisting of Aerosil ® R805 ( CAS 92797-60-9 ), Aerosil ® R202 ( CAS 67762-90-7 or CAS 541-02-6 ), CAB-O-SIL TS 720 ( CAS 67762-90-7 ), Aerosil ® R8200 ( CAS 68909-20-6 ), Aerosil ® R812 ( CAS 68909-20-6
  • Hydrophobic Aerosils such as Aerosil ® R805 ( CAS 92797-60-9 ), Aerosil ® R202 ( CAS 67762-90-7 or CAS 541-02-6 ), CAB-O-SIL TS 720 ( CAS 67762-90-7 ), Aerosil ® R8200 ( CAS 68909-20-6 ), Aerosil ® R812 ( CAS 68909-20-6 ), Aerosil ® R972 ( CAS 68611-44-9 ), and Aerosil ® R974 ( CAS 68611-44-9 ), are especially preferred in the epoxide paste because under certain circumstances, mainly depending on the overall composition of the respective epoxide paste, said hydrophobic Aerosils offer an additional stabilizing effect of the respective epoxide paste.
  • the dental root canal filling composition is substantially free, preferably completely free, of a compound of the following formula (I) wherein
  • the dental root canal filling composition is substantially free, preferably completely free, of a compound having one of the following formulas:
  • the at least one di- or polyepoxide is a compound of the following formula (II): wherein
  • Q represents an (m+1)-valent organic group.
  • Q represents a 2-valent organic group, or a 3-valent organic group, and more preferably, Q represents a 2-valent organic group.
  • the (m+1)-valent organic group may be a group having a total of 1 to 40 carbon atoms, preferably 2 to 20 carbon atoms.
  • the organic group may include an aliphatic, alicyclic, or aromatic moiety or a combination of two or more of such moieties.
  • the organic group may further include one or more functional groups such as amide groups, ester groups, urethane groups, urea groups, keto groups, ether groups, thioether groups, carbonate groups, or tertiary amino groups, which link two or more aliphatic, alicyclic, or aromatic moieties.
  • the organic group may be substituted by one or more substituents selected from hydroxyl groups, halogen atoms, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkylthio group, a C 6-10 aryl group, a C 6-10 aryloxy group, a C 7-14 arylalkyl group, or a C 7-14 arylalkoxy group.
  • substituents selected from hydroxyl groups, halogen atoms, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkylthio group, a C 6-10 aryl group, a C 6-10 aryloxy group, a C 7-14 arylalkyl group, or a C 7-14 arylalkoxy group.
  • the (m+1)-valent organic group may include alicyclic or aromatic moiety, and more preferably the (m+1)-valent organic group includes an aromatic moiety.
  • Q represents the following group:
  • n is an integer of from 1 to 3.
  • m is an integer of from 1 to 2, and more preferably m is 1.
  • R 6 , R 7 and R 10 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C 1-6 alkyl group.
  • R 6 , R 7 and R 10 represent a hydrogen atom.
  • all three of R 6 , R 7 and R 10 represent a hydrogen atom.
  • the R 8 , R 9 and R 11 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C 1-6 alkyl group. Furthermore, in a compound of formula (II), if more than one R 8 is present, the more than one R 8 may be different. In a compound of formula (II), if more than one R 9 is present, the more than one R 9 may be different. In a compound of formula (II), if more than one R 11 is present, the more than one R 11 may be different.
  • R 8 , R 9 and R 11 represent a hydrogen atom. In a particularly preferred embodiment, all of the R 8 , R 9 and R 11 moieties which are present are hydrogen atoms.
  • the compound according to formula (II) is Bisphenol A Diglycidylether ( CAS: 25068-38-6 ), or Bis-[4-(-2,3-epoxypropoxy)phenyl]-methane ( CAS: 9003-36-5 ).
  • the dental root canal filling composition further comprises an aliphatic polyamine selected among compounds of the following structures: wherein
  • R 12 is hydrogen, a substituted or unsubstituted C 3-18 cycloalkyl group, or a C 7-18 arylalkyl group. More preferably, R 12 is a substituted or unsubstituted C 3-18 cycloalkyl group, or a substituted or unsubstituted C 7-18 arylalkyl group. Even more preferably, R 12 is a substituted or unsubstituted C 7-18 arylalkyl group. In a particularly preferred embodiment, R 12 is an unsubstituted C 7-18 arylalkyl group.
  • R 13 is difunctional substituted or unsubstituted C 1 to C 18 alkylene group, more preferably R 13 is a difunctional unsubstituted C 1 to C 18 alkylene group.
  • A' is a moiety derived from a compound that is capable of an addition reaction with amines such as di- or polyepoxides.
  • A' is a moiety derived from an addition reaction of a di- or polyepoxide according to formula (II) and an amine. More preferably, A' is a moiety derived from an addition reaction of an amine with a compound of formula (II) which is a diepoxide.
  • A' is a moiety derived from an addition reaction of an amine and a compound of formula (II) which is a diepoxide, and wherein in the compound of formula (II) Q represents the following structures:
  • c is an integer.
  • c is an integer of from 1 to 10, more preferably c is an integer of from 2 to 8, even more preferably c is an integer of from 4 to 6.
  • the dental root canal filling composition further comprises at least one radio-opaque particulate filler, preferably at least CaWO 4 as the at least one particulate filler.
  • the radiopaque particulate filler usually has an average particle size of from 0.005 to 100 ⁇ m, preferably of from 0.01 to 40 ⁇ m as measured using, for example, by electron microscopy or by using a conventional laser diffraction particle sizing method as embodied by a MALVERN Mastersizer S or MALVERN Mastersizer 2000 apparatus.
  • the radiopaque particulate filler may be a multimodal radiopaque particulate filler representing a mixture of two or more radiopaque particulate fractions having different average particle sizes.
  • the radiopaque particulate filler may also be a mixture of particles of different chemical composition.
  • the radiopaque filler in the form of a particulate filler or a nanofiller may be selected from any of the zinc, ytterbium, yttrium, gadolinium, zirconium, strontium, tungsten, tantalum, thorium, niobium, barium, bismuth, molybdenum and lanthanum metals, alloys thereof, organometallic complexes thereof, oxides, sulfates, carbonates, halides, oxy-halides, subnitrates, tungstates and carbides thereof, iodine and inorganic iodides, either singly or in combination.
  • the radiopaque filler is selected from any of bismuth trioxide, bismuth carbonate, bismuth oxy-chloride, bismuth subnitrate, zirconium oxide, barium sulfate, barium tungstate and calcium tungstate, either singly or in combination.
  • the radiopaque filler is selected from barium tungstate and calcium tungstate, either singly or in combination.
  • the radiopaque filler is calcium tungstate.
  • the dental composition according to the present invention preferably comprises 1 to 85 percent by weight, more preferably 40 to 85 percent by weight, even more preferably 40 to 70 percent by weight, of the radiopaque particulate filler, based on the weight of the entire composition.
  • the viscosity and thixotropicity of the uncured as well as the physical properties of the cured compositions may be controlled by varying the sizes and surface areas of the filler.
  • the filler may be surface treated with one or more silanating agents.
  • Preferred silanating agents include those having at least one polymerizable double bond and at least one group that easily hydrolyses with water. Examples of such agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl-dimethoxy-monochlorosilane, 3-methacryloxypropyldichloromonomethoxysilane, methacryloxypropyltri-chlorosilane, 3-methacryloxypropyldichloromonomethylsilane, 3- methacryloxypropylmonochlorodimethylsilane, or 2,3-epoxypropyltri-methoxysilane, aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane and mixtures thereof.
  • the present invention also claims the use of such an inventive dental root canal filling composition for a treatment or a prevention of an endodontic disease.
  • a storage-stable two-pack dental root canal filling composition comprising a first paste and a second paste, wherein the dental root canal filling composition is a composition as defined by one of the preceding claims 1 to 6.
  • the storage-stable two-pack dental root canal filling composition is provided in a double chamber cartridge, wherein said double chamber cartridge is made of a polymeric material, preferably made of polypropylene or polybutyleneterephthalate, especially preferred made of polybutyleneterephthalate.
  • the double chamber cartridge out of polybutyleneterephthalate, which provides in general superior barrier properties (compared to polypropylene) of the two chambers against possible oxygen migration; and especially against the migration of coloring components of the amine paste composition into the chamber material.
  • the at least one di- or polyepoxides have a dynamic viscosity at 23 °C of less than 30 Pa * s.
  • the dental root canal filling composition has a gelation time of less than 25 hours, preferably less than 20 hours, and more preferably less than 16 hours.
  • the dental root canal filling composition has a glass transition temperature T g ranging from 38 to 80°C, preferably from 39 to 60°C, and more preferably from 40 to 50°C.
  • the present invention thus addresses the problem of providing a suitable alternative of primary monoamines as part of a dental root canal filling composition, which allows mimicking of the characteristic AH Plus paste properties in terms of setting kinetics, thermomechanical behavior and handling properties (flow, film thickness).
  • TCD represents a TCD diamine of the following formula:
  • DSC Densired Scanning Calorimetry
  • the cured samples were portioned to individual masses of 4.5 - 5.5 mg and transferred into aluminum crucibles (diameter: 6 mm) for DSC characterization.
  • Measurements were performed on a DSC 204 F1 Phoenix (Netzsch-Gedorfebau GmbH) using a heat flow of 30 K/min for heating and cooling cycles. Analysis was performed using the software Netsch Measurement, Netsch ASC Manager (auto sampling), Netsch Proteus (analysis).
  • the mixed pastes exhibit a gelation time of less than 15 h (method described above), flow of 22 mm (according to ISO 6876:2012), film thickness of 17 ⁇ 2 ⁇ m (according to ISO 6876:2012).
  • 2-(3-Methylbutyl)cyclopentane-1-amine (0.4939 g, 3.1807 mmol), N,N'-dibenzyl-5-oxanonandiamin-1,9 (OPC-91; 1.1125 g, 3.2671 mmol), TCD-Amine (0.0649 g, 0.3340 mmol), CaWO 4 (6.4223 g), ZrO 2 (1.6080 g), Aerosil ® 200 (0.1955 g) and Baysilone M-500 (0.1051 g) were transferred into a speed mixer container and mixed for 5 min with 2150 rpm. The paste was manually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm) to afford a homogenous, white paste.
  • Epoxide Paste A1 and Amine Paste A1 were mixed in a ratio of 1.0000:1.1103 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 15 h 20 min (SAR5-50-01), flow (according to ISO6876:2012): 21.2 mm (SAR5-51-01), film thickness (according to ISO6876:2012): 10 ⁇ m (SAR5-52-01). Glass transition temperature (cured for 2 weeks at 37°C): 45.8 °C (MAW1-15-01).
  • Epoxide Paste A2 and Amine Paste A2 were mixed in a ratio of 1.0000:1.0335 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5-29-02), flow (according to ISO6876:2012): 23.0 mm (SAR5-25-01), film thickness (according to ISO6876:2012): 17 ⁇ m (SAR5-27-02). Glass transition temperature (cured for 2 weeks at 37°C): 47.3 °C (MAW1-16-01).
  • Cyclopentylamine (0.7400 g, 8.6905 mmol), OPC-91 (1.6679 g, 4.8981 mmol), TCD-Amine (0.0996 g, 0.5126 mmol), CaWO 4 (9.6335 g), ZrO 2 (2.4128 g), Aerosil ® 200 (0.2921 g) and Baysilone M-500 (0.1618 g) were transferred into a speed mixer container and mixed for 5 min with 2150 rpm. The paste was manually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm) to afford a homogenous, white paste.
  • Epoxide Paste A3 and Amine Paste A3 were mixed in a ratio of 1.0000:0.8110 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5-30-04), flow (according to ISO6876:2012): 21.8 mm (SAR5-27-01), film thickness (according to ISO6876:2012): 9 ⁇ m (SAR5-29-02). Glass transition temperature (cured for 2 weeks at 37°C): 41.8 °C (MAW1-16-01).
  • Epoxide Paste A4 and Amine Paste A4 were mixed in a ratio of 1.0000:1.1104 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 15 h 20 min (SAR5-50-02), flow (according to ISO6876:2012): 20.0 mm (SAR5-51-02), film thickness (according to ISO6876:2012): 9 ⁇ m (SAR5-52-02). Glass transition temperature (cured for 2 weeks at 37°C): 44.9 °C (MAW1-17-01).
  • Epoxide Paste A5 and Amine Paste A5 were mixed in a ratio of 1.0000:0.9518 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5-30-01), flow (according to ISO6876:2012): 21.2 mm (SAR5-26-01), film thickness (according to ISO6876:2012): 14 ⁇ m (SAR5-28-01). Glass transition temperature (cured for 2 weeks at 37°C): 42.6 °C (MAW1-18-01).
  • Cycloheptylamine (0.7415 g, 6.5504 mmol), OPC-91 (1.6683 g, 4.8993 mmol), TCD-Amine (0.0949 g, 0.4884 mmol), CaWO 4 (9.6321 g), ZrO 2 (2.4120 g), Aerosil ® 200 (0.2935 g) and Baysilone M-500 (0.1585 g) were transferred into a speed mixer container and mixed for 5 min with 2150 rpm. The paste was manually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm) to afford a homogenous, white paste.
  • Epoxide Paste A6 and Amine Paste A6 were mixed in a ratio of 1.0000:0.9518 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5-30-02), flow (according to ISO6876:2012): 21.8 mm (SAR5-26-02), film thickness (according to ISO6876:2012): 13 ⁇ m (SAR5-28-02). Glass transition temperature (cured for 2 weeks at 37°C): 42.6 °C (MAW1-18-01).
  • Cyclooctylamine (0.7415 g, 5.8280 mmol), OPC-91 (1.6677 g, 4.8975 mmol), TCD-Amine (0.0981 g, 0.5049 mmol), CaWO 4 (9.6344 g), ZrO 2 (2.4145 g), Aerosil ® 200 (0.2926 g) and Baysilone M-500 (0.1583 g) were transferred into a speed mixer container and mixed for 5 min with 2150 rpm. The paste was manually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm) to afford a homogenous, white paste.
  • Epoxide Paste A7 and Amine Paste A7 were mixed in a ratio of 1.0000:1.0105 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 14 h 5 min (SAR5-30-03), flow (according to ISO6876:2012): 20.5 mm (SAR5-26-03), film thickness (according to ISO6876:2012): 8 ⁇ m (SAR5-28-03). Glass transition temperature (cured for 2 weeks at 37°C): 44.2 °C (MAW1-19-01).
  • Epoxide Paste A8 and Amine Paste A8 were mixed in a ratio of 1.0000:1.0838 m(epoxide paste)/m(amine paste).
  • the gel time at 37 °C was 15 h 20 min (SAR5-50-03), flow (according to ISO6876:2012): 20.3 mm (SAR5-51-03), film thickness (according to ISO6876:2012): 8 ⁇ m (SAR5-52-03). Glass transition temperature (cured for 2 weeks at 37°C): 48.9 °C (MAW1-19-01).
  • the paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yellow paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 21 mm, film thickness of 13 mm (all according to ISO 6876) and glass transition temperature of 45 ⁇ 2 °C (DSC) after curing for 2 weeks at 37°C.
  • Epoxide resins and cellulose ester / ether is dispersed in T range from 40 - 100°C. Clear resins can be achieved within 10 min - 10 h. Ultra-turrax agitation can used to promote dispensing.
  • Epoxide Premixture 1 (4.349 g) and CaWO4 (10.589 g), Aerosil ® 200 (0.042 g) and SICOVIT ® (Yellow 10 E172) (0.021 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yellow paste.
  • Amine resin and cellulose ether is dispersed in T range from 40 - 120°C. Clear resins can be achieved within 10 min - 12 h. Ultra-turrax agitation can used to promote dispensing.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 22 mm, film thickness of 16 mm (all according to ISO 6876) and glass transition temperature of 44 ⁇ 2 °C (DSC, after curing for 2 weeks at 37°C.
  • Epoxide Premixture 1 (4.349 g) and CaWO4 (10.589 g), Aerosil R202 (0.042 g) and SICOVIT ® (Yellow 10 E172) (0.021 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yellow paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 22 mm, film thickness of 16 mm (all according to ISO 6876) and glass transition temperature of 45 ⁇ 2 °C (DSC, after curing for 2 weeks at 37°C.
  • Epoxide Premixture 1 (4.349 g) and CaWO4 (10.589 g), Aerosil 200 (0.042 g) and SICOVIT ® (Yellow 10 E172) (0.021 g) were added and speed mixing was applied (5 min, 2150 rpm). The paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yellow paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 22 mm, film thickness of 16 mm (all according to ISO 6876) and glass transition temperature of 47 ⁇ 2 °C (DSC, after curing for 2 weeks at 37°C.
  • the paste was manually mixed with a spatula followed by another speed mixer run (3 min, 2150 rpm) to afford a homogenous, light yellow paste.
  • the mixed pastes exhibit a gelation time of less than 15 h, flow of 23 mm, film thickness of 13 mm (all according to ISO 6876) and glass transition temperature of 46 ⁇ 2 °C (DSC) after curing for 2 weeks at 37°C.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dental Preparations (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)

Claims (8)

  1. Zahnwurzelkanalfüllungszusammensetzung, umfassend
    (i) mindestens ein Di- oder Polyepoxid;
    (ii) 1-Aminotetralin; und
    (iii) mindestens ein Diamin.
  2. Zahnwurzelkanalfüllungszusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass das mindestens eine Diamin der Zahnwurzelkanalfüllungszusammensetzung ein disekundäres Diamin oder ein primäres Diamin ist, wobei die Zahnwurzelkanalfüllungszusammensetzung vorzugsweise mindestens ein primäres Diamin und mindestens ein disekundäres Diamin umfasst.
  3. Zahnwurzelkanalfüllungszusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zahnwurzelkanalfüllungszusammensetzung ferner mindestens einen rheologischen Zusatzstoff und/oder ein rheologisches Modifikationsmittel umfasst, wie etwa Ethylcellulose und Celluloseacetatbutyrat.
  4. Zahnwurzelkanalfüllungszusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das mindestens eine Di- oder Polyepoxid eine Verbindung mit folgender Formel (II) ist:
    Figure imgb0027
     wobei
    Q eine (m+1)-valente organische Gruppe ist,
    R6, R7 und R10, die gleich sein oder sich unterscheiden können und die unabhängig voneinander sind, für ein Wasserstoffatom oder eine C1-6-Alkylgruppe stehen,
    R8, R9 und R11, die gleich sein oder sich unterscheiden können und die unabhängig voneinander sind, für ein Wasserstoffatom oder eine C1-6-Alkylgruppe stehen,
    m eine ganze Zahl von 1 bis 3 ist.
  5. Zahnwurzelkanalfüllungszusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zahnwurzelkanalfüllungszusammensetzung ferner ein aliphatisches Polyamin umfasst, ausgewählt aus Verbindungen der folgenden Strukturen:
    Figure imgb0028
    Figure imgb0029
    Figure imgb0030
     wobei
    R12 ein Wasserstoff oder eine substituierte oder unsubstituierte C1-18-Alkylgruppe, eine substituierte oder unsubstituierte C3-18-Cycloalkylgruppe oder eine substituierte oder unsubstituierte C7-18-Aryalkylgruppe ist,
    R13 eine difunktionelle substituierte oder unsubstituierte C1- bis C18-Alkylengruppe oder eine substituierte oder unsubstituierte Cycloalkylengruppe ist,
    A' ein Anteil ist, der aus einer zu einer Additionsreaktion mit Aminen, wie etwa Dioder Polyepoxiden, fähigen Verbindung abgeleitet wurde, und
    c eine ganze Zahl ist.
  6. Zahnwurzelkanalfüllungszusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zahnwurzelkanalfüllungszusammensetzung ferner mindestens ein strahlenundurchlässiges partikelförmiges Füllmaterial umfasst, vorzugsweise mindestens CaWO4 als das mindestens eine partikelförmige Füllmaterial.
  7. Zahnwurzelkanalfüllungszusammensetzung nach einem der vorhergehenden Ansprüche zur Verwendung bei der Behandlung oder Vorbeugung einer endodontischen Erkankung.
  8. Lagerstabile Zahnwurzelkanalfüllungszusammensetzung im Doppelpack, umfassend eine erste Paste und eine zweite Paste, wobei die Zahnwurzelkanalfüllungszusammensetzung eine Zusammensetzung gemäß der Definition nach einem der vorhergehenden Ansprüche 1 bis 6 ist.
EP20833819.4A 2019-12-17 2020-12-17 Zahnwurzelkanalfüllungszusammensetzung Active EP4076336B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19217246 2019-12-17
PCT/EP2020/086720 WO2021122957A1 (en) 2019-12-17 2020-12-17 Dental root canal filling composition

Publications (2)

Publication Number Publication Date
EP4076336A1 EP4076336A1 (de) 2022-10-26
EP4076336B1 true EP4076336B1 (de) 2024-05-15

Family

ID=68944370

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20833819.4A Active EP4076336B1 (de) 2019-12-17 2020-12-17 Zahnwurzelkanalfüllungszusammensetzung

Country Status (7)

Country Link
US (1) US20230014155A1 (de)
EP (1) EP4076336B1 (de)
JP (1) JP2023506909A (de)
CN (1) CN114929178A (de)
AU (1) AU2020410373A1 (de)
CA (1) CA3164598A1 (de)
WO (1) WO2021122957A1 (de)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE9802360D0 (sv) * 1998-07-01 1998-07-01 Wikstroem Hakan Vilhelm New 2-aminothiazol-fused 2-aminoindans and 2-aminotetralins ((basic)-N-substituted and (basic)-N,N-disubstituted derivatives of 2,6-diamino-thiazolo(4,5-f)indan and 2,7-di-amino-thiazolo(4,5-g)tetralin
DE102012003117A1 (de) * 2012-02-16 2013-08-22 Heinrich-Heine-Universität Düsseldorf Antimikrobielle Füllmaterialmischung
ES2784676T3 (es) * 2014-07-02 2020-09-29 Dentsply Detrey Gmbh Composición dental
US20160297745A1 (en) * 2014-09-24 2016-10-13 Apotex Inc. Endodontic post system
EP3721857A1 (de) * 2019-04-11 2020-10-14 Dentsply DeTrey GmbH Dentale zusammensetzung

Also Published As

Publication number Publication date
CN114929178A (zh) 2022-08-19
WO2021122957A1 (en) 2021-06-24
EP4076336A1 (de) 2022-10-26
AU2020410373A1 (en) 2022-06-16
CA3164598A1 (en) 2021-06-24
JP2023506909A (ja) 2023-02-20
US20230014155A1 (en) 2023-01-19

Similar Documents

Publication Publication Date Title
JP4344026B2 (ja) 光誘導されたカチオン硬化を起こす組成物及びそれらの使用
JP3098995B2 (ja) 室温硬化性シリコーン材料およびその使用
CN105708713B (zh) 一种牙科用窝沟封闭剂及其制备方法
EP4076336B1 (de) Zahnwurzelkanalfüllungszusammensetzung
WO2007038764A2 (en) Epoxy based oil free root canal sealer
AU2020271270B2 (en) Dental composition
CA2551229C (en) Dental root canal filling material
EP3721858B1 (de) Dentalzusammensetzung
JP7189337B2 (ja) 硬化性歯科用二剤組成物
Yusoff et al. Hardness of flowable resin composite from rice husk
M Yusoff et al. Hardness of Flowable Resin Composite from Rice Husk/Nazrul M. Yusoff...[et al.]

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220628

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20230512

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230524

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20240125

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020031063

Country of ref document: DE